Sulphuric acid derivatives of organic acid amides



Patented Dec. 6, 1938 UNITED STATES SULPHURIC ACID DERIVATIVES OF OR- GANIG ACID AllflDES Erich Rosenhauer, Dusseldorf-Benrath, Germany, assignor to the firm Henkel & Cie. G. m. b. 11., Dusseldorf, Germany No Drawing. Application April 27, 1934, Serial No. 722,686. In Germany May 12, 1933 9 Claims.

It has been found that a new class of valuable substances may be obtained by treating with sulphonating agents amides having at least one group capable of being sulphonated, of the general formula ZX-R-NY, where R signifies an aliphatic carbonyl group containing not more than 3 carbon atoms or aliphatic sulphonyl group containing not more than 3 carbon atoms, X a non-metallic polyvalent atom of the group consisting of oxygen, sulphur and nitrogen, Z an aliphatic, cycloaliphatic, or aromatic radical containing not more than carbon atoms, and NY an amido group substituted by at least one higher. non-aromatic hydrocarbon radical Y containing at least 6 carbon atoms.

For the process according to the present invention, amides, substituted at the nitrogen, of aliphatic oxy, mercapto or amino carboxylic or sulphonic acids, substituted at the oxygen, sulphur or nitrogen are employed as starting substances. The following general formulae may be proposed for these compounds:

(2) Z-S-R-NY (3) ZZ"-N-R-NY.

The compounds according to Formulae l and 2 constitute amides of substituted oxy or mercapto acids, and those according to the Formula 3 constitute amides of secondary or tertiary aminoacids, which may contain the amino-nitrogen combined in any desired manner, for example in secondary, tertiary or ring form. In these derivatives of amides, the organic radicals Z, Z and Z" signify aliphatic, cycloaliphatic and aromatic radicals. Suitable radicals are for example the ethyl, c-oxy-ethyl, acetyl, cyclohexyl and phenyl radicals. R represents the radicals of methane, ethane, propane acids and their homologues, such as lauric acid, and also the radicals of the corresponding sulphonic acids, such as ethane, propane and octodecane sulphonic acids. The amido-residue NS; contains higher aliphatic or cycloaliphatic hydrocarbon radicals. Such residues are fatty alkyl radicals, such as the decyl and undecyl residue, the dodecyl, tetradecyl and octodecenyl radical, as well as the corresponding radicals of alcohols obtained by the reduction of other soap-forming carboxylic acids, such as resinic acids and naphthenic acids. The said derivatives of amides contain a reactive group capable of being sulphonated, Such groups are free hydroxyl groups and carbon double bonds.

The said reactive amides may be obtained for example by reacting halogen acyl amides, substituted at the nitrogen by a higher aliphatic or cycloaliphatic residue, with alcohols, mercaptans or primary or secondary amines. Thus tit- 3,7-

dioxypropyl oxy-lauric-N-cyclohexy1-amide is obtained from iz-bromo-lauric-N-cyclohexylamide and the monosodium compound of glycerol, or B-phenoxy-ethane-sulphonic-N-methyldodecyl amide from p1-chlorethane-sulphonic-N- methyl-dodecyl amide and sodium 'phenolate. Furthermore, tolyl-mercapt'o-ethane sulphonic- N-hexadecyl-amide is obtained from bromoethane-sulphonic-N-hexadecyl-amide and sodium tolylmercaptan. In a similar manner, anilino-acetic-N-undecylamide is obtained from monobromacetic-N-undecyl amide and aniline. Finally, the starting substances for the present process may also be obtained by the reaction of organic oxy, mercapto or amino acids, which are substituted at the oxygen, sulphur or nitrogen by an organic radical, with higher aliphatic or cycloaliphatic primary or secondary amines. In this case the acids are employed as such or in the form of their functional derivatives, such as esters, anhydrides, acid halides, lactones and the like. By this process, for example, phenylamino-acetic-N-cyclohexyl-amide is obtained from phenyl amino acetic methyl ester and cyclohexylamine, and (hydroxy-ethoxy) -acetic- N-undecyl-amide is obtained from the lactone of (hydroxy-ethoxy) -acetic acid and undecylamine.

According to the nature of the organic radicals and the sulphonating agent both true sulphonic acids and also sulphuric esters are formed in treating the amides described with sulphonating agents; some of the starting substances absorb both groups simultaneously. The sulphuric acid radical may enter both the amide group and also the acid group and the organic substituents.

As sulphonating agents are employed: strong sulphuric acid, sulphuric acid containing $0 ,503 and its additive products with organic compounds, chlorosulphonic acid and the like sulphonating agents,it being expedient to work in the presence of solvents, diluents and dehydrating agents, but in some cases these may be omitted.

The water-soluble products obtained according to the present invention may be employed as soap substitutes, and also in the pharmaceutical and cosmetic industries.

Examples hydroxy-ethoxy-acetic acid and the amine mixture thus obtained, a mixture of the hydroxyethoxy-acetic amides substituted at the nitrogen by higher aliphatic radicals is obtained.

42 parts by weight of the amide mixture are dissolved in 200 parts by volume of ether and 20 parts by weight of chlorosulphoniq acid are added at a temperature of to C. with good agitation. Agitation is continued until a test sample of the sulphonation product is clearly soluble in water. After neutralization with soda and working up, the sodium salts of the mixture of acid sulphuric esters of the higher hydroxy-ethoxyacetic-N-alkylamides are obtained in the form of a white powder which dissolves in water to form clear solutions. The substance is absolutely stable to hard water and exhibits a very good foam-producing and wetting power.

(2) 20 parts by weight of phenoxyacetic-N- cyclohexyl-amide are heated on the water bath for about 2 hours with the same quantity by weight of concentrated sulphuric acid. The re action product is poured into ice water, is neutralized with soda and salted out with common salt. The resulting sodium salt of the monosulphonic acid of phenoxyacetic-N-cyclohexylamide is, in the dry condition, a powder which dissolves in water to form clear solutions.

(3) 20 parts by weight of a mixture of the amides of phenoxyacetic acid and a mixture of higher aliphatic amines, which have been obtained from the amides of coconut fatty acids by Hofmanns reaction, are heated on the water bath with the same quantity by weight of sulv phuric acid for about half an hour. The reaction product is poured into ice water, neutralized with soda and salted out with common salt. The resulting sodium salt of a mixture of sulphonic. acids of phenoxyacetic-N-alkylamides is a white powder which dissolves in cold water to form clear solution having a good foam-producing power.

I claim:

1. The process for the manufacture of sulphuric acid derivatives of organic acid amides, which comprises treating with sulphonating agents amides having at least one group capable of being sulphonated, of the general formula ZX-R-NY, where R is selected from the group consisting of aliphatic carbonyl groups containing not more than 3 carbon atoms and aliphatic sulphonyl groups containing not more than 3 carbon atoms, X is a non-metallic, polyvalent atom of the group consisting of oxygen, sulphur and nitrogen, combined with at least one hydrocarbon group Z containing not more than carbon atoms, and NY is an amido group substituted by at least one higher non-aromatic hydrocarbon radical Y containing at least six carbon atoms.

2. The process for the manufacture of sulphuric acid derivatives of organic acid amides, which comprises treating with sulphonating agents, amides having at least one free hydroxyl group, of the general formula ZX-R-NY, where R is selected from the group consisting of aliphatic carbonyl groups containing not more than three carbon atoms and aliphatic sulphonyl groups containing not more than three carbon atoms, X is a non-metallic, polyvalent atom of the group consisting of oxygen, sulphur and nitrogen, combined with at least one hydrocarbon group Z containing not more than ten carbon atoms, and NY is an amido group substituted by at least one higher non-aromatic hydrocarbon radical Y containing at least six carbon atoms.

3. The process for the manufacture of sulphuric acid derivatives of organic acid amides, which comprises treating with sulphonating agents, amides having at least one acyclic carbon double bond, of the general formula ZX-R-NY, where R is selected from the group consisting of aliphatic carbonyl groups containing not more than three carbon atoms and aliphatic sulphonyl groups containing not more than three carbon atoms, X is a non-metallic polyvalent atom of the group consisting of oxygen, sulphur and nitrogen, combined with at least one hydrocarbon group Z containing not more than ten carbon atoms, and NY is an amido-group substituted by at least one higher non-aromatic hydrocarbon radical Y containing at least six carbon atoms.

4. The process for the manufacture of sulphuric acid derivatives of organic acid amides, which comprises treating with sulphonating agents, amides having at least one cyclic carbon double bond, of the general formula ZX-R-NY, where R is selected from the group consisting of aliphatic carbonyl groups containing not more than three carbon atoms and aliphatic sulphonyl groups containing not more than three carbon atoms, X is a non-metallic, polyvalent atom of the group consisting of oxygen, sulphur and nitrogen, combined with at least one hydrocarbon group Z containing not more than ten carbon atoms, and NY is an amido-group substituted by at least one higher non-aromatic hydrocarbon radical Y containing at least six carbon atoms.

5. The process for the manufacture of sulphuric acid derivatives of organic acid amides, which comprises treating with sulphonating agents, aliphatic carboxylic acid amides having at least one group capable of being sulphonated at the general formula ZX-R-NY, where R is selected from the group consisting of aliphatic carbonyl groups containing not more than three carbon atoms, X a non-metallic polyvalent atom of the group consisting of oxygen, sulphur and nitrogen, combined with at least one hydrocarbon group Z containing not more than ten carbon atoms, and NY an amido-group substituted by at least one higher non-aromatic hydrocarbon radical Y containing at least six carbon atoms.

6. The process for the manufacture of sulphuric acid derivatives of organic acid amides,

which comprises treating with sulphonatingagents, aliphatic sulphonic acid amides having at least one group capable of being sulphonated, of the general formula ZX-R-NY, where R is selected from the group consistingof aliphatic sulphonyl groups containing not more than three carbon atoms, X is a non-metallic polyvalent atom of the group consisting of oxygen, sulphur and nitrogen, combined with at least one hydrocarbon group Z containing not more than ten carbon atoms, and NY is an amido-group substituted by at least one higher non-aromatic hydrocarbon radical Y containing at least six carbon atoms.

7. The process for the manufacture of sulphuric acid derivatives of organic acid amides, which comprises treating with sulphonating agents, amides having at least one group capable of being sulphonated, of the general formula ZX-R-NY, where R is selected from the group consisting of aliphatic carbonyl. groups containing not more than three carbon atoms and aliphatic sulphonyl groups containing not more than three carbon atoms, X an oxygen atom combined with a hydrocarbon group Z- containing not more than ten carbon atoms, and NY is an amido-group substituted by at least one higher non-aromatic hydrocarbon radical Y containing at least six carbon atoms.

8. The process for the manufacture of sulphuric acid derivatives of organic acid amides, which comprises treating with sulphonating agents, amides having at least one group capable of being sulphonated, of the general formula ZX-R-NY, where'R is selected from the group consisting of aliphatic carbonyl groups containing not more than three carbon atoms and allphatic sulphonyl groups containing not more than three carbon atoms, X is a non-metallic polyvalent atom of the group consisting of oxygen, sulphur and nitrogen, combined with at least one hydrocarbon radical Z containing not more than ten carbon atoms, and NY is an amidogroup substituted by at least one higher aliphatic hydrocarbon radical Y containing at least six carbon atoms.

consisting of aliphatic carbonyl groups contain ing not more than three carbon atoms and aliphatic sulphonyl groups containing not more than three carbon items, X is a non-metallic polyvalent atom of the group consisting of oxy-.

gen, sulphur and nitrogen, combined with at least one hydrocarbon group Z containing not more than 10 carbon atoms, and NY is an amidogroup substituted by at least one higher cycloaliphatic hydrocarbon radical Y containing at least six carbon atoms.

ERICH ROSEBSI'HAUER. 

